Xanthenone-yl esters of phosphoric and phosphonic acids

ABSTRACT

Disclosed are new compounds of the formula ##STR1## wherein R 1  and R 2  are each independently selected from the group consisting of halogen, alkyl, haloalkyl, nitro, alkylsulfinyl, alkylsulfonyl and cyano; k and m are integers from 0 to 3; Q is selected from the group consisting of oxygen and sulfur; Y is selected from the group consisting of oxygen and sulfur R 3  is selected from the group consisting of alkyl and ##STR2## wherein R 5  is selected from the group consisting of halogen, alkyl, haloalkyl, nitro and cyano; n is an integer from 0 to 3; R 4  is selected from the group consisting of alkyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino and ##STR3## wherein R 6  is selected from the group consisting of halogen, alkyl, haloalkyl, nitro, and cyano; p is an integer from 0 to 3; and A and B are each independently selected from the group consisting of oxygen and sulfur, with the proviso that, if R 4  is alkoxy, then one of A and B must be sulfur. 
     Further disclosed is the insecticidal utility of the foregoing compounds.

This invention related to new compositions of matter and morespecifically relates to new chemical compounds of the formula ##STR4##wherein R¹ and R² are each independently selected from the groupconsisting of halogen, alkyl, haloalkyl, nitro, alkylsulfinyl,alkylsulfonyl and cyano; k, and m are integers from 0 to 3; Q isselected from the group consisting of oxygen and sulfur; Y is selectedfrom the group consisting of oxygen and sulfur; R³ is selected from thegroup consisting of alkyl and ##STR5## wherein R⁵ is selected from thegroup consisting of halogen, alkyl, haloalkyl, nitro and cyano; n is aninteger from 0 to 3; R⁴ is selected from the group consisting of alkyl,alkoxy, alkylthio, amino, alkylamino, dialkylamino and ##STR6## whereinR⁶ is selected from the group consisting of halogen, alkyl, haloalkyl,nitro, and cyano; and p is an integer from 0 to 3;

and A and B are each independently selected from the group consisting ofoxygen and sulfur, with the proviso that, if R⁴ is alkoxy, then one of Aand B must be sulfur.

These compounds are useful as insecticides.

In a preferred embodiment of this invention, R¹ and R² are eachindependently selected from the group consisting of halogen, loweralkyl, lower haloalkyl, nitro, lower alkylsulfinyl, lower alkylsulfonyl,and cyano; k and m are integers from 0 to 3; Q is selected from thegroup consisting of oxygen and sulfur; Y is selected from the groupconsisting of oxygen and sulfur; R³ is selected from the groupconsisting of lower alkyl and ##STR7## wherein R⁵ is selected from thegroup consisting of halogen, lower alkyl, lower haloalkyl, nitro andcyano, n is an integer from 0 to 3; R⁴ is selected from the groupconsisting of lower alkyl, lower alkoxy, lower alkylthio, amino loweralkylamino, di(lower alkyl) amino and ##STR8## wherein R⁶ is selectedfrom the group consisting of halogen, lower alkyl, lower haloalkyl,nitro and cyano; p is an integer from 0 to 3; and A and B are eachindependently selected from the group consisting of oxygen and sulfur,with the proviso that, if R⁴ is alkoxy, then one of A and B must besulfur.

The term "lower" as used herein designates a straight or branched carbonchain of up to six carbon atoms.

The compounds of this invention can be made by reacting a compound ofthe formula ##STR9## wherein R¹, R², k and m, Q, and Y are ashereinbefore described, with a compound of formula ##STR10## wherein R³,R⁴, A and B are as hereinbefore described. This reaction can be effectedby dissolving or slurrying, in an inert reaction medium such asacetonitrile or tetrahydrofuran, the compound of formula II togetherwith an acid acceptor such as potassium carbonate or triethylamine. Tothis solution/slurry is then added, with stirring, at a temperature offrom about 0° C. to 40° C., the compound of formula III. The reactionmixture may be stirred for a period of several hours after the additionto ensure completeness of reaction, the acid-acceptor salts can then befiltered off and the desired product isolated and purified by standardtechniques.

The compound of formula II wherein Y is oxygen can be prepared by thefollowing reaction sequence: ##STR11## wherein R¹, R², k, m, and Q areas hereinabove described.

The alkoxy group of the compound of formula V may be any lower alkoxybut preferably is methoxy. Also, the formula V compound must have atleast one hydrogen ortho to the --QH group.

The position of the hydroxyl group of the formula II compound isdetermined by the position of the alkoxy group relative to the --QHgroup of the formula V compound, thus this compound is selected to givea formula II compound having the desired structure. However, when bothpositions ortho to the --QH group of the formula V compound arehydrogen, a mixture of position isomers of the formula VII compound, andthus of the formula II compound, are produced. These isomers can beseparated and the desired isomer of the formula II compound isolated byart-known methods such as fractional crystallization, differentialsolubilization, high performance liquid chromatography and the like.

In carrying out the above reaction sequence, the compounds of formula IVand V are dissolved in an inert reaction medium such as 1-pentanol, acopper catalyst (preferably prepared according to the method of P. H.Gore and G. K. Huges, Journal of the Chemical Society, 1615(1959),wherein copper metal is precipitated from copper sulfate solution byzinc dust) and potassium carbonate are added and the mixture is stirredand heated, at the reflux temperature of the solvent, for a period offrom about 0.5 to about 8 hours.

Treatment of uncyclized condensation product, the formula VI compound,with concentrated sulfuric acid effects its cyclization to the compoundof formula VII. An inert reaction medium, such as acetyl chloride isused, the reaction is carried out at room temperature or slightlyelevated temperatures for a period of from about 0.5 to 2 hours.

The compound of formula II is generally known in the art and may beprepared by treatment of the compound of formula VII, in an inertreaction medium such as toluene, with anhydrous aluminum chloride at atemperature of from 80° C. to 90° C. for a period of from about 2 to 4hours. Hydrochloric acid, at a concentration of about 6 N is then addedand the mixture stirred at a temperature of from 80° C. to 90° C. for aperiod of from about 2 to 4 hours.

The compound of formula II wherein Y is sulfur may be prepared by thereaction sequence: ##STR12## wherein R¹, R², k, m, and Q are asheretofore described. The compound of formula VII is mixed, with nodiluents, with P₂ S₅ and heated to a temperature of from about 130° C.to 140° C. for a period of from about 0.5 to 4 hours. The unreacted P₂S₅ is removed by hydrolysis with water; the compound of formula IX maythen be recrystallized using, for example, ethanol. The formula Xcompound may be prepared by treating the formula IX compound withanhydrous aluminum chloride as described hereinabove for the preparationof the formula II compound from the formula VII compound.

Exemplary compounds of formula III suitable for preparing the compoundsof the present invention are O-ethyl S-propyl phosphorochloridothiolate;O-ethyl S-propyl phosphorochloridothiolothionate; O-(2,4-dicyanophenyl)S-propyl phosphorochloridothiolate; O-(3,4,5-trichlorophenyl S-propylphosphorochloridothiolothionate; S-ethyl S-propylphosphorochloridothiolate; S-butyl S-pentylphosphorochloridodithiolothionate; S-pentylethylphosphonochloridothiolate; S-(3-nitrophenyl) (3-chlorophenyl)phosphonochloridothiolothionate; O-(2,3-dimethylphenyl) S-butylphosphorochloridothiolate; O-ethyl O-butyl phosphorochloridothionate;O-(4-chloro-5-methylphenyl) O-propyl phosphorochloridothionate; O-ethylS-propyl phosphorochloridothiolothionate; O-ethylethylphosphonochloridothiolate; O-ethylN,N-diemthylphosphoramidochloridate; S-propylN,N-diethylphosphoramidochloridothiolate; S-pentylN,N-dihexylphosphoramidothiolothionate; O-butylN-butylphosphoramidochloridate; S-hexyl phosphoramidochloridothiolateand the like.

Exemplary compounds of formula IV suitable for preparation the compoundsof the present invention are 2-chlorobenzoic acid;2-chloro-3-cyanobenzoic acid; 2-chloro-4,5-dimethylbenzoic acid;2,3,5-trichlorobenzoic acid; 2-chloro-4-(trifluoro-methyl) benzoic acid;2-chloro-2-methyl-3-ethylsulfinylbenzoic acid;2,3,4-trichloro-4-ethyl-sulfonylbenzoic acid;2,4-dichloro-3-methyl-4-chloro-5-cyanobenzoic acid;2-chloro-5-nitrobenzoic acid and the like.

Exemplary compounds of formula V suitable for preparing the compounds ofthis invention are 2-methoxyphenol; 2-methoxy-3,4-dichlorophenol;2-methoxy-4,5-dimethylphenol; 2-methoxy-5-nitrophenol;2-methoxy-3-(trifluoromethyl)phenol; 2-methoxy-4-ethylsulfinylphenol;2-methoxy-3,5-dicyanophenol; 2-methoxy-3,4,5-tribromophenol;2-methoxy-4-ethylsulfonylphenol; 2-methoxy-4-cyanobenzenethiol;2-methoxy-3,4-dinitrobenzenethiol;2-methoxy-3-trichloromethyl-4-ethylbenzenethiol;2-methoxy-4-ethylsulsulfinylbenzenethiol;2-methoxy-4-methyl-5-propylsulfonylbenzenethiol;2-methoxy-3,4-dichlorobenzenethiol; 3-methoxy-4-bromophenol;3-methoxy-5,6-dinitrophenol; 3-methoxy-4,5-dicyanophenol;3-methoxy-4-butylsulfinylphenol;3-methoxy-5-ethyl-6-(trifluoromethyl)phenol;3-methoxy-4-propylsulfonyl-phenol; 2,5-dibromo-3-methoxyphenol;3-methoxyphenol; 2,4-dichloro-3-methoxybenzenethiol;2,5-dicyano-3-methoxybenzenethiol;3-methoxy-5-butylsulfonylbenzenethiol;3-methoxy-4,5,6-trichloro-benzenethiol;2-trifluoromethyl-3-methoxybenzenethiol;3-methoxy-5-butylsulfinylbenzenethiol; 4-methoxyphenol;2-chloro-3-ethyl-4-methoxyphenol; 3-nitro-4-methoxyphenol;2-(1-ethylpropyl)-3-cyano-4-methoxyphenol; 2,3-dibutyl-4-methoxyphenol;3-ethylsulfonyl-4-methoxyphenol; 4-methoxy- 5-butylsulfonylphenol;4-methoxy-5-trifluoromethylphenol;2,3-dichloro-5-(2-ethylbutyl)benzenethiol;3-cyano-4-methoxybenzenethiol; 2-ethyl-3-(trifluoromethyl)benzenethiol;3-nitro-4-methoxybenzenethiol; 2-propylsulfinyl-4-methoxybenzenethiol;3-bromo-4-methoxy-5-ethylsulfonylbenzenethiol and the like.

EXAMPLE 1 PREPARATION OF O,O-Diethyl O-(Xanthen-9-one-2-yl)Phosphorothionate

2-Hydroxyxanthen-9-one (1.0 gram; 0.0047 mole),O,O-diethyl-phosphorochloridothionate (0.89 grams; 0.0049 mole),acetonitrile (25 ml) and potassium carbonate (1.94 grams; 0.0047 mole)were charged into a glass reaction vessel fitted with a mechanicalstirrer and thermometer. The reaction mixture was then stirred at atemperature of from about 40° C. to 45° C. for a period of about 16hours. A precipitate formed which was filtered off, washed withacetonitrile and the washings added to the filtrate. An equal volume ofacetonitrile was added to the combined acetonitrile solutions and silicagel (2 grams) added and the slurry stirred at room temperature for aperiod of about 1.5 hours. The silica gel was filtered off, the filtratewas treated with activated charcoal, refiltered and the solvent strippedoff on a rotary evaporator (70° C., 15 mm Hg) to give a brown oil. Thisoil was dissolved in a 1/1 mixture of chloroform/cyclohexane (16 ml),silica gel (2 grams) was added and the slurry was stirred for 2.5 hoursat room temperature. The silica gel was filtered off, washed withtoluene and the washings combined with the filtrate. Solvent was thenstripped from the filtrate to yield the desired product O,O-diethylO-(xanthen-9-one-2-yl) phosphorothionate.

Elemental analysis; Theory: C=56.04%; H=4.70%; P=8.50%. Found: C=55.76%;H=4.73%; P=8.5%.

EXAMPLE 2 PREPARATION OF O-Ethyl O-(Xanthen-9-one-2-yl) S-PropylPhosphorothiolate

2-Hydroxyxanthen-9-one (1.4 grams; 0.0066 mole) was slurried inmethylene chloride (10 ml) and added dropwise over about a 5 minutesperiod to a solution of O-ethyl S-propyl phosphorochloridothiolate inmethylene chloride (15 ml), at a temperature of about 0° C., containedin a glass reaction vessel fitted with a mechanical stirrer andthermometer. The reaction mixture was then cooled to about -65° C. andtriethylamine (0.67 grams) in methylene chloride (2 ml) added. Thereaction mixture was stirred at a temperature of about 10° C. for aperiod of about 2 hours. After holding at room temperature for a periodof about 16 hours, the mixture was diluted with an equal volume ofmethylene chloride and this solution washed with cold H₂ O (3-30 mlportions), dried with phase separation paper, treated with activatedcarbon and filtered. The solvent was stripped off on a rotary evaporator(70° C., 15 mm Hg) to yield a brown oil which solidified. This oil wasadded to 5 volumes of diisopropyl ether and the mixture heated toreflux, cooled and filtered. The ether was stripped off in a rotaryevaporator to yield a yellow oil. The yellow oil was dissolved in asolvent comprised of 60 volumes chloroform, 40 volumes cyclohexane.Silica gel (2 grams) was added to this solution and the mixture wasstirred for a period of about 1 hour at room temperature, then filtered.The silica gel was washed with 60/40 v/v chloroform/cyclohexane (1.0 ml)and the washings combined with the filtrate. Solvent was partiallystripped off with a rotary evaporator, and the concentrate waschromatographed on a silica gel column using as eluent 40/60 v/v ethylacetate/cyclohexane. The fractions containing the desired product wereidentified by infrared and NMR analysis. These fractions were combinedand the solvent stripped off on a rotary evaporator to yield the desiredproduct O-ethyl O-(xanthen-9-one-2-yl) S-propyl phosphorothiolate as alight yellow oil which crystallized on standing.

Elemental analysis; Theory: C=57.13%; H=5.06%; P=8.19%. Found: C=57.13%;H=5.10%; P=7.75%.

EXAMPLE 3 PREPARATION OF O-Phenyl O-(Xanthen-9-one-2-yl) S-PropylPhosphorothiolate

2-Hydroxyxanthen-9-one (0.01 mole), acetonitrile (25 ml) and potassiumcarbonate (0.01 mole) are charged into a glass reaction vessel fittedwith a mechanical stirrer and thermometer. O-Phenyl S-propylphosphorochloridothiolate (0.01 mole) in acetonitrile (6 ml) is addeddropwise, with stirring, at room temperature. The reaction mixture isstirred for a period of about 48 hours at a temperature of from about35° C. to 50° C. It is then cooled to room temperature and filtered.Solvent is stripped from the filtrate using a rotary evaporator (70° C.,15 mm Hg). The devolatilized residue is redissolved in 1/1 v/vchloroform/cyclohexane (25 ml). This solution is then slurried withsilica gel (2 grams) at room temperature for a period of about 2 hours,then filtered. Solvent is stripped from the filtrate using a rotaryevaporator to yield the desired product O-phenyl O-(xanthen-9-one-2-yl)S-propyl phosphorothiolate.

EXAMPLE 4 PREPARATION OF O-(Xanthen-9-one-2-yl) S-Nitrophenyl) S-PropylPhosphorodithiolate

2-Hydroxyxanthen-9-one (0.01 mole), acetonitrile (25 ml) and potassiumcarbonate (0.01 mole) are charged into a glass reaction vessel fittedwith a mechanical stirrer and thermometer. S-(4-Nitrophenyl) S-propylphosphorochloridodithiolate (0.01 mole) in acetonitrile (6 ml) is addeddropwise, with stirring, at room temperature. The reaction mixture isstirred for a period of about 48 hours at a temperature of from about35° C. to 50° C. It is then cooled to room temperature and filtered.Solvent is stripped from the filtrate using a rotary evaporator (70° C.,15 mm Hg). The devolatilized residue is redissolved in 1/1 v/vchloroform/cyclohexane (25 ml). This solution is then slurried withsilica gel (2 grams) at room temperature for a period of about 2 hours,then filtered. Solvent is stripped from the filtrate using a rotaryevaporator to yield the desired product O-(xanthen-9-one-2-yl)S-(nitrophenyl) S-propyl phosphorodithiolate.

EXAMPLE 5 PREPARATION OF O-Ethyl O-(Xanthen-9-thione-2-yl) S-PropylPhosphorothiolothionate

2-Hydroxyxanthen-9-thione (1.97 grams; 0.009 mole) and acetonitrile (120ml) were charged into a glass reaction vessel fitted with a mechanicalstirrer, thermometer and reflux condenser, and the xanthenethione putinto solution by heating to reflux for a period of about 1 hour. Thesolution was cooled to room temperature, then treated with activatedcarbon, filtered, and charged into a glass reaction vessel fitted with amechanical stirrer and thermometer. Potassium carbonate (1.2 grams) andO-ethyl S-propyl phosphorochloridothiolothionate (1.74 grams) were addedto the reaction vessel and the mixture was stirred at a temperature offrom about 30° C. to 35° C. for a period of about 24 hours. The reactionmixture was then warmed to a temperature of about 50° C. and stirred foran additional period of about 7 hours. The reaction mixture was filteredand the solvent was stripped from the filtrate using a rotary evaporator(70° C., 15 mm Hg) to give an oil. This oil was dissolved in a solventcomprised of 6.5 volumes chloroform, 93.5 volumes cyclohexane (40 ml);silica gel (4 grams) was added and the mixture stirred at roomtemperature for a period of about 2.5 hours. The solution was filtered,the filtrate treated with activated carbon and refiltered. The solventwas stripped off on a rotary evaporator to yield the desired productO-ethyl O-(xanthen-9-thione-2-yl) S-propyl phosphorothiolothionate.

Elemental Analysis: Theory: C=52.67; H=4.66; p=7.55. Found: C=52.25;H=4.68; P=7.37.

EXAMPLE 6 PREPARATION OF O-(Xanthen-9-thione-2-yl) S-EthylPhenylphosphonothiolate

2-Hydroxyxanthen-9-thione (0.01 mole), acetonitrile (25 ml) andpotassium carbonate (0.01 mole) are charged into a glass reaction vesselfitted with a mechanical stirrer and thermometer. S-Ethylphenylphosphonochloridothiolate (0.01 mole) in acetonitrile (6 ml) isadded dropwise, with stirring, at room temperature. The reaction mixtureis stirred for a period of about 48 hours at a temperature of from about35° C. to 50° C. It is then cooled to room temperature and filtered.Solvent is stripped from the filtrate using a rotary evaporator (70° C.,15 mm Hg). The devolatilized residue is redissolved in 1/1chloroform/cyclohexane (25 ml). This solution is then slurried withsilica gel (2 grams) at room temperature for a period of about 2 hours,then filtered. Solvent is stripped from the filtrate using a rotaryevaporator to yield the desired product O-(xanthen-9-thione-2-yl)S-ethyl phenylphosphonothiolate.

EXAMPLE 7 PREPARATION OF O-Ethyl O-(Xanthen-9-thione-2-yl) S-PropylPhosphorothiolate

2-Hydroxyxanthen-9-thione (0.01 mole), acetonitrile (25 ml) andpotassium carbonate (0.01 mole) are charged into a glass reaction vesselfitted with a mechanical stirrer and thermometer. O-Ethyl S-propylphosphorochloridothiolate (0.01 mole) in acetonitrile (6 ml) is addeddropwise, with stirring, at room temperature. The reaction mixture isstirred for a period of about 48 hours at a temperature of from about35° C. to 50° C. It is then cooled to room temperature and filtered.Solvent is stripped from the filtrate using a rotary evaporator (70° C.,15 mm Hg). The devolatilized residue is redissolved in 1/1chloroform/cyclohexane (25 ml). This solution is then slurried withsilica gel (2 grams) at room temperature for a period of about 2 hours,then filtered. Solvent is stripped from the filtrate using a rotaryevaporator to yield the desired product O-ethylO-(xanthen-9-thione-2-yl) S-propyl phosphorothiolate.

EXAMPLE 8 PREPARATION OF O-Ethyl O-(Xanthen-9-one-3-yl) S-PropylPhosphorothiolothionate

3-Hydroxyxanthen-9-one (1.48 grams; 0.007 moles) and acetonitrile (20ml) were charged into a glass reaction vessel fitted with a mechanicalstirrer and thermometer. To this mixture, at room temperature, was addedpotassium carbonate (0.97 grams, 0.007 mole) and a solution of O-ethylS-propyl phosphorochloridothiolothionate (1.41 grams; 0.007 mole) inacetonitrile. The reaction mixture was stirred for a period of about 54hours at a temperature of about 50° C. The reaction mixture was cooledto room temperature and filtered. The filtered-off solid was washed withacetonitrile (10 ml) and the washings combined with filtrate. Thecombined filtrate/washings were concentrated on a rotary evaporator togive a yellow brown oil. This oil was dissolved in acetone (5 ml),cyclohexane (95 ml) was added, then 5 grams of silica gel. The mixturewas stirred for a period of 1 hour at room temperature, filtered, thesilica gel washed with 5/95 v/v acetone/cyclohexane, the washingscombined with the filtrate and the solvent removed from the combinedfiltrate/washings on a rotary evaporator to yield the desired productO-ethyl O-(xanthen-9-one-3-yl) S-propyl phosphorothiolothionate as ayellow oil.

Elemental Analysis; Theory: C=54.86%; H=4.85%; P=7.85%. Found: C=55.57%,H=4.99%, P=7.41.

EXAMPLE 9 PREPARATION OF O-Ethyl O-(Xanthen-9-one-3-yl)S-(3,5-Dichlorophenyl)phosphorothiolothionate

3-Hydroxyxanthen-9-one (0.01 mole), acetonitrile (25 ml) and potassiumcarbonate (0.01 mole) are charged into a glass reaction vessel fittedwith a mechanical stirrer and thermometer. O-EthylS-(3,5-dichlorophenyl)phosphorothiolothionate (0.01 mole) inacetonitrile (6 ml) is added dropwise, with stirring, at roomtemperature. The reaction mixture is stirred for a period of about 48hours at a temperature of from about 35° C. to 50° C. It is then cooledto room temperature and filtered. Solvent is stripped from the filtrateusing a rotary evaporator (70° C., 15 mm Hg). The devolatilized residueis redissolved in 1/1 v/v chloroform/cyclohexane (25 ml). This solutionis then slurried with silica gel (2 grams) at room temperature for aperiod of about 2 hours, then filtered. Solvent is stripped from thefiltrate using a rotary evaporator to yield the desired product O-ethylO-(xanthen-9-one-3-yl) S-(3,5-dichlorophenyl)phosphorothiolothionate.

EXAMPLE 10 PREPARATION OF O-(Xanthen-9-one-4-yl) S-PhenylPhenylphosphonothiolothionate

4-Hydroxyxanthen-9-one (0.01 mole), acetonitrile (25 ml) and potassiumcarbonate (0.01 mole) are charged into a glass reaction vessel fittedwith a mechanical stirrer and thermometer. S-Phenylphenylphosphonochloridothiolothionate. (0.01 mole) in acetonitrile (6ml) is added dropwise, with stirring, at room temperature. The reactionmixture is stirred for a period of about 48 hours at a temperature offrom about 35° C. to 50° C. It is then cooled to room temperature andfiltered. Solvent is stripped from the filtrate using a rotaryevaporator (70° C., 15 mm Hg). The devolatilized residue is redissolvedin 1/1 v/v chloroform/cyclohexane (25 ml). This solution is thenslurried with Silica Gel (2 grams) at room temperature for a period ofabout 2 hours, then filtered. Solvent is stripped from the filtrateusing a rotary evaporator to yield the desired productO-(xanthen-9-one-4-yl) S-phenyl phenylphosphonotiolotionate.

EXAMPLE 11 PREPARATION OF O-Ethyl O-(Xanthen-9-one-4-yl)(2,4,6-Trichlorophenyl)phosphonate

4-Hydroxyxanthen-9-one (0.01 mole), acetonitrile (25 ml) and potassiumcarbonate (0.01 mole) are charged into a glass reaction vessel fittedwith a mechanical stirrer and thermometer. O-Ethyl(2,4,6-trichlorophenyl)phosphonochloridate (0.01 mole) in acetonitrile(6 ml) is added dropwise, with stirring, at room temperature. Thereaction mixture is stirred for a period of about 48 hours at atemperature of from about 35° C. to 50° C. It is then cooled to roomtemperature and filtered. Solvent is stripped from the filtrate using arotary evaporator (70° C., 15 mm Hg). The devolatilized residue isredissolved in 1/1 v/v chloroform/cyclohexane (25 ml). This solution isthen slurried with silica gel (2 grams) at room temperature for a periodof about 2 hours, then filtered. Solvent is stripped from the filtrateusing a rotary evaporator to yield the desired product O-ethylO-(xanthen-9-one-4-yl) (2,4,6-trichlorophenyl)phosphonate.

EXAMPLE 12 PREPARATION OF O-Ethyl O-(3,6-Dimethylxanthen-9-one-2-yl)S-Propyl Phosphorothiolothionate

2-Hydroxy-3,6-dimethylxanthen-9-one (0.01 mole), acetonitrile (25 ml)and potassium carbonate (0.01 mole) are charged into a glass reactionvessel fitted with a mechanical stirrer and thermometer. O-EthylS-propyl phosphorochloridothiolothionate (0.01 mole) in acetonitrile (6ml) is added dropwise, with stirring, at room temperature. The reactionmixture is stirred for a period of about 48 hours at a temperature offrom about 35° C. to 50° C. It is then cooled to room temperature andfiltered. Solvent is stripped from the filtrate using a rotaryevaporator (70° C., 15 mm Hg). The devolatilized residue is redissolvedin 1/1 v/v chloroform/cyclohexane (25 ml). This solution is thenslurried with silica gel (2 grams) at room temperature for a period ofabout 2 hours, then filtered. Solvent is stripped from the filtrateusing a rotary evaporator to yield the desired product O-ethylO-(3,6-dimethylxanthen-9-one-2-yl) S-propyl phosphorothiolothionate.

EXAMPLE 13 PREPARATION OF O-(3,6-Dimethylxanthen-9-one-2-yl) S-Ethyl(2,6-Dicyanophenyl)phosphonothiolothionate

2-Hydroxy-3,6-dimethylxanthen-9-one (0.01 mole), acetonitrile (25 ml)and potassium carbonate (0.01 mole) are charged into a glass reactionvessel fitted with a mechanical stirrer and thermometer. S-Ethyl(2,6-dicyanophenyl)phosphonochloridothiolothionate (0.01 mole) inacetonitrile (6 ml) is added dropwise, with stirring, at roomtemperature. The reaction mixtire is stirred for a period of about 48hours at a temperature of from about 35° C. to 50° C. It is then cooledto room temperature and filtered. Solvent is stripped from the filtrateusing a rotary evaporator (70° C., 15 mm Hg). The devolatilized residueis redissolved in 1/1 v/v chloroform/cyclohexane (25 ml). This solutionis then slurried with silica gel (2 grams) at room temperature for aperiod of about 2 hours, then filtered. Solvent is stripped from thefiltrate using a rotary evaporator to yield the desired productO-(3,6-dimethylxanthen-9-one-2-yl) S-ethyl(2,6-dicyanophenyl)phosphonothiolothionate.

EXAMPLE 14 PREPARATION OF O-Hexyl O-(3-Nitroxanthen-9-one-4-yl)S-(2-Methyl-4-bromophenyl)Phosphorothiolothionate

3-Nitro-4-hydroxyxanthen-9-one (0.01 mole), acetonitrile (25 ml) andpotassium carbonate (0.01 mole) are charged into a glass reaction vesselfitted with a mechanical stirrer and thermometer. O-HexylS-(2-methyl-4-bromophenyl)phosphorochloridothiolothionate (0.01 mole) inacetonitrile (6 ml) is added dropwsie, with stirring, at roomtemperature. The reaction mixture is stirred for a period of about 48hours at a temperature of from about 35° C. to 50° C. It is then cooledto room temperature and filtered. Solvent is stripped from the filtrateusing a rotary evaporator (70° C., 15 mm Hg). The devolatilized residueis redissolved in 1/1 v/v chloroform/cyclohexane (25 ml). This solutionis then slurried with silica gel (2 grams) at room temperature for aperiod of about 2 hours, then filtered. Solvent is stripped from thefiltrate using a rotary evaporator to yield the desired product O-hexylO-(3-nitroxanthen-9-one-4-yl)S-(2-methyl-4-bromophenyl)phosphorothiolothionate.

EXAMPLE 15 PREPARATION OF O-(3-Nitroxanthen-9-one-4-yl) S-Ethyl(4-Trifluoromethylphenyl)phosphonothiolothionate

3-Nitro-4-hydroxyanthen-9-one (0.01 mole), acetonitrile (25 ml) andpotassium carbonate (0.01 mole) are charged into a glass reaction vesselfitted with a mechanical stirrer and thermometer. S-Ethyl(4-trifluoromethylphenyl)phosphonochloridothiolothionate (0.01 mole) inacetonitrile (6 ml) is added dropwise, with stirring, at roomtemperature. The reaction mixture is stirred for a period of about 48hours at a temperature of from about 35° C. to 50° C. It is then cooledto room temperature and filtered. Solvent is stripped from the filtrateusing a rotary evaporator (70° C., 15 mm Hg). The devolatilized residueis redissolved in 1/1 v/v chloroform/cyclohexane (25 ml). This solutionis then slurried with silica gel (2 grams) at room temperature for aperiod of about 2 hours, then filtered. Solvent is stripped from thefiltrate using a rotary evaporator to yield the desired productO-(3-nitroxanthen-9-one-4-yl) S-ethyl(4-trifluromethylphenyl)phosphonothiolothionate.

EXAMPLE 16 PREPARATION OF O-Ethyl O-(4-Cyanoxanthen-9-one-3-yl)4-Chlorophenylphosphonothionate

1-Hydroxy-4-nitro-6-cyanoxanthen-9-one (0.01 mole), acetonitrile (25 ml)and potassium carbonate (0.01 mole) are charged into a glass reactionvessel fitted with a mechanical stirrer and thermometer. O-Ethyl(4-chlorophenyl)phosphonochloridothionate (0.01 mole) in acetonitrile (6ml) is added dropwise, with stirring, at room temperature. The reactionmixture is stirred for a period of about 48 hours at a temperature offrom about 35° C. to 50° C. It is then cooled to room temperature andfiltered. Solvent is stripped from the filtrate using a rotaryevaporator (70° C., 15 mm Hg). The devolatilized residue is redissolvedin 1/1 v/v chloroform/cyclohexane (25 ml). This solution is thenslurried with silica gel (2 grams) at room temperature for a period ofabout 2 hours, then filtered. Solvent is stripped from the filtrateusing a rotary evaporator to yield the desired product O-ethylO-(4-nitro-6-cyanoxanthen-9-one-1-yl) 4-chlorophenylphosphonothionate.

EXAMPLE 17 PREPARATION OF O-Ethyl O-(Thioxanthen- 9-one-2-yl) S-PropylPhosphorothiolothionate

2-Hydroxythioxanthen-9-one (2.28 grams; 0.01 mole), acetonitrile (60 ml)and potassium carbonate (1.38 grams; 0.01 mole) were charged into aglass reaction vessel fitted with a mechanical stirrer and thermometer.O-Ethyl S-propyl phosphorochloridothiolothionate (2.18 grams; 0.01 mole)in acetonitrile (3 ml) was added dropwise, with stirring, at roomtemperature. The reaction mixture was stirred for a period of about 30hours at room temperature. After this time the reaction mixture wasfiltered and the filtrate stripped of solvent using a rotary evaporator.The residue was then column chromatographed using silica gel and a 25/75mixture of ethyl acetate and cyclohexane. The eluant is stripped ofsolvent to yield the desired product O-ethyl O-(thioxanthen-9-one-2-yl)S-propyl phosphorothiolothionate as an oil.

EXAMPLE 18 PREPARATION OF O-Ethyl O-(Thioxanthen-9-one-2-yl) S-PropylPhosphorothiolate

2-Hydroxythioxanthene-9-one (2 grams; 0.009 mole), toluene (25 ml)tetrahydrofuran (25 ml) and triethylanine (0.89 grams) were charged intoa reaction vessel equipped with stirrer and thermometer. The mixture wascooled to 0° C. and O-ethyl S-propyl phosphorochloridothiolate (0.009mole) dissolved in toluene (16 ml) was added dropwise with stirring.After the addition was completed, the mixture was allowed to stand atroom temperature overnight. The mixture was then filtered, stripped ofsolvent and the residue was column chromatographed using a 40/60 ethylacetate-cyclohexane mixture. The eluant was stripped of solvents toyield the desired product. O-ethyl O-(thioxanthen-9-one-2-yl) S-propylphosphorothiolate as an oil which solidified upon standing to a solidmelting at 57° to 60° C.

Additional compounds within the scope of this invention which can beprepared according to the procedures of the foregoing examples areO-ethyl O-(5-trifluoromethylxanthen-9-one-2-yl) S-propylphosphorothiolothionate; O-(2-chlorophenyl)O-(7-ethylsulfonylxanthen-9-one-2-yl) S-propyl phosphorothiolothionate;O,O-dipropyl O-(6-butylsulfinylxanthen-9-one-2-yl)phosphorothionate;O-ethyl O-(2-chloro-7-nitroxanthen-9-one-4-yl) S-propylphosphorothiolothionate; O-(3-nitrophenyl)O-(2-chloro-6-nitro-7-ethylxanthen-9-one-4-yl) S-propylphosphorothionate; O-ethyl O-(3-chloroxanthen-9-one-2-yl) S-propylphosphorothiolate; O-ethyl O-(xanthen-9-thione-2-yl) S-propylphosphorothiolothionate; O-ethyl O-(3-chloroxanthen-9-thione-2-yl)S-propyl phosphorothiolate; O-(3,4-dimethyl-7-cyanoxanthen-9-one-1-yl)S-pentyl S-hexyl phosphorothiolothionate; O-ethylO-(4-ethylsulfinyl-8-ethylxanthen-9-one-2-yl) S-propylphosphorothiolothionate; O-hexylO-(1,4,6,7-tetramethylxanthen-9-one-3-yl) S-butyl phosphorothiolate;O-(2,7-dicyanoxanthen-9-one-4-yl) S-ethyl phenylphosphonothiolothionate;O-ethyl O-(2-nitro-6,7-dichloroxanthen-9-one-2-yl) S-propylphosphorothiolothionate; O-(1,4-dimethyl-5,8-dinitroxanthen-9-one-3-yl)S-ethyl S-propyl phosphorothiolothionate;O-(6,7-dimethylxanthen-9-thione-2-yl) S-ethyl S-propylphosphorodithiolothionate;O-(4-nitro-5-cyano-6-chloroxanthen-9-thione-1-yl) S-butyl S-pentylphosphorodithiolothionate; O-ethylO-(1,4-dipropyl-6,7-dichloroxanthen-9-thione-2-yl) S-propylphosphorothiolothionate; O-methylO-(4-cyano-6,7-dichloroxanthen-9-thione-3-yl) S-butyl phosphorothionate;O-(6,7,8-trimethylxanthen-9-thione-4yl) S-ethyl S-butylphosphorodithiolate; O-ethyl O-(4-trifluoromethylxanthen-9-thione-2-yl)S-propyl phosphorothiolothionate; O-ethylO-(6-ethylsulfonylxanthen-9-thione-1-yl) S-propylphosphorothiolothionate; O-(8-propylsulfinylxanthen-9-thione-2-yl)S,S-dipropyl phosphorodithiolothionate; O-ethyl O-(xanthen-9-one-2-yl)S-propyl phorothiolothionate; O-pentylO-(2-ethyl-6-chloroxanthen-9-one-1-yl) S-propyl phosphorothiolothionate;O-ethyl O-(5-chloroxanthen-9-one-2-yl) N,N-dimethylphosphoramidate;O-(6-methylxanthen-9-one-2-yl) S-butylN,N-dipentylphosphoramidothiolate; O-(8-ethylsulfinylxanthen-9-one-2-yl)S-hexyl N-propylphosphoramidothiolate; O-(2-butylxanthen-9-one-2-yl)S-propyl phosphoramidothiolothionate and the like.

For practical use as insecticides, the compounds of this invention aregenerally incorporated into insecticidal compositions which comprise aninert carrier and an insecticidally toxic amount of such a compound.Such insecticidal compositions, which can also be called formulations,enable the active compound to be applied conveniently to the site of theinsect infestation in any desired quantity. These compositions can besolids, such as dusts, granules or wettable powders; or they can beliquids such as solutions, aerosols or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the talcs, clays, silicas,pyrophyllite and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water and/or oil to anydesired concentration of the active compound, can be prepared byincorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvent such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofinsecticides can be dispersed under superatmospheric pressure asaerosols. However, preferred liquid insecticidal compositions areemulsifiable concentrates, which comprise an active compound accordingto this invention and as the inert carrier, a solvent and an emulsifier.Such emulsifiable concentrates can be extended with water and/or oil toany desired concentration of active compound for application as spraysto the site of the insect infestation. The emulsifiers most commonlyused in these concentrates are nonionic or mixture of nonionic withanionic surface-active agents.

A typical insecticidal composition according to this invention isillustrated by the following example, in which the quantities are inparts by weight.

EXAMPLE 19

    ______________________________________                                        Preparation of a Dust                                                         ______________________________________                                        Product of Example 1                                                                             10                                                         Powdered talc      90                                                         ______________________________________                                    

The above ingredients are mixed in a mechanical grinder-blender and areground until a homogeneous, freeflowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the insect infestation.

The compounds of this invention can be applied as insecticides in anymanner recognized by the art. One method for destroying insectscomprises applying to the locus of the insect infestation, aninsecticidal composition comprising an inert carrier and, as theessential active ingredient, in a quantity which is toxic to saidinsects, a compound of the present invention. The concentration of thenew compounds of this invention in the insecticidal compositions willvary greatly with the type of formulation and the purpose for which itis designed, but generally the insecticidal compositions will comprisefrom about 0.05 to about 95 percent by weight of the active compounds ofthis invention. In a preferred embodiment of this invention, theinsecticidal compositions will comprise from about 5 to 75 percent byweight of the active compound. The compositions can also comprise suchadditional substances as other pesticides, stabilizers, spreaders,deactivators, adhesives, stickers, fertilizers, activators, synergistsand the like.

The compounds of the present invention are also useful when combinedwith other insecticides in the insecticidal compositions heretoforedescribed. These other insecticides can comprise from about 5 to 95percent of the active ingredients in the insecticidal compositions. Useof the combinations of these other insecticides with the compounds ofthe present invention provide insecticidal compositions which are moreeffective in controlling insects and often provide results unattainablewith separate compositions of the individual insecticides. The otherinsecticides with which the compounds of this invention can be used inthe insecticidal compositions to control insects, can includehalogenated compounds such as DDT, methoxychlor, TDE, lindane,chlordane, isobenzan, aldrin, dieldrin, heptachlor, endrin, mirex,endosulfon, dicofol and the like; organic phosphorus compounds such asTEPP, schradan, ethion, parathion, methyl parathion, PEN, demeton,carbophenothion phorate, zinophos, diazinon, malathion, mevinphos,dimethoate, DBD, ronnel, oxydemeton-methyl, dicapthon, chlorothion,phosphamidon, naled, fenthion, trichlorofon, DDVP and the like; organicnitrogen compounds such as dinitro-O-cresol, dinitrocyclohexylphenol,DNB, DNP, binapacril, azobenzene and the like; organic carbamatecompounds such as carbaryl, ortho 5353 and the like; organic sulfurcompounds such as phenothiazine, phenoxathin, lauryl thiocyanate,bis(2-thiocyanoethyl)ether, isobornyl thiocyanoacetate and the like; aswell as such substances usually referred to as fumigants, as hydrogencyanide, carbon tetrachloride, calcium cyanide, carbon disulfide,ethylene dichloride, propylene dichloride, ethylene dibromide, ethyleneoxide, methyl bromide, paradichlorobenzene and the like.

The compounds of the present invention can also be combined withfungicidal and nematocidal chemical compounds to form pesticidalcompositions useful for the control of fungi and in some cases soilnematodes as well as insects. Typical examples of such fungicidalchemical compounds are ferbam, nabam, zineb, ziram, thiram, chloranil,dichlone, glyodin, cycloheximide, dinocap, maneb, captan, dodine, PCNB,p-dimethylaminobenzenediazo sodium sulfonate and the like; whileexamples of nematocidal compounds are chloropicrin O,O-diethylO-(2,4-dichlorophenyl) phosphorothioate, tetrachlorothiophene, dazomet,dibromochloropropane and the like.

The new compounds of this invention can be used in many ways for thecontrol of insects. Insecticides which are to be used as stomach poisonsor protective materials can be applied to the surface on which theinsects feed or travel. Insecticides which are to be used as contactpoisons or eradicants can be applied directly to the body of the insect,as a residual treatment to the surface on which the insect may walk orcrawl, or as a fumigant treatment of the air which the insect breathes.In some cases, the compounds applied to the soil or plants surfaces aretaken up by the plant, and the insects are poisoned systemically.

The above methods of using insecticides are based on the fact thatalmost all the injury done by insects is a direct or indirect result oftheir attempts to secure food. Indeed, the large number of destructiveinsects can be classified broadly on the basis of their feeding habits.Among the insects which can be effectively controlled by the compoundsof the present invention are the chewing insects, such as the Mexicanbean beetle and the southern armyworm; the piercing-sucking insects,such as the pea aphid, the cereal leaf beetle, the housefly, the grapeleafhopper, the chinch bug, the lygus bug, the oyster shell scale, theCalifornia red scale, the Florida red scale, the soft scale andmosquitoes; the internal feeders, including borers, such as the Europeancorn borer, the peach twig borer and the corn earworm, worms of weevilssuch as the codling moth, the alfalfa weevil, the cotton boll weevil,the pink boll worm, the plum curculio, the red banded leaf roller, themelonworm, the cabbage looper and the apple maggot, leaf miners such asthe apple leaf miner, the birch leaf miner and the beet leaf miner, andgall insects such as the wheat joint worm and the grape phylloxera.Insects which attack below the surface of the ground are classified assubterranean insects and include such destructive pests as the woollyapple aphid, the Japanese beetle, the onion maggot and the cornrootworm.

The quantity of active compound of this invention to be used for insectcontrol will depend on a variety of factors, such as the specific insectinvolved, intensity of the infestation, weather, type of environment,type of formulation and the like. For example, the application of onlyone or two ounces of active chemical per acre may be adequate forcontrol of a light infestation of an insect under conditions unfavorablefor its feeding, while a pound or more of active compound per acre maybe required for the control of a heavy infestation of insects underconditions favorable to their development.

The insecticidal activity of the compounds of the present invention wasdemonstrated by experiments carried out for the control of a variety ofinsects. The desired quantity of the test compound (the coquantity beingdetermined by the application concentration or application rate to beused in later testing) is dissolved or dispersed in a solvent consistingof acetone containing 3.19 grams/liter of Triton X-155® (alkylarylpolyether alcohol). When it has dissolved or dispersed in the acetone, 4volumes of the acetone solution or dispersion are diluted with 96volumes of distilled water. (If the test compound is insoluble in theacetone or distilled water it can be dispersed using a tissue grinder.)Lower concentration test solutions may be made by dilution of higherconcentration solutions with a diluent consisting of 96 volumesdistilled water and 4 volumes of acetone containing 3.19 grams of TritonX 155® per liter.

Test plants used in these experiments are prepared by planting theappropriate seeds in sterilized soil contained in plastic pots having anupper soil surface area of approximately 12.25 square inches (a squarepot having a 3.5 inch side). After the seed has been planted, a layer ofapproximately 0.25 inches of sand is spread on the top surface of thesoil. The test compound is applied after the plant has reached aspecified size.

For foliar applications, the test compound, dissolved or dispersed inthe water/acetone solvent described above, is sprayed as a mist onto thefoliage of the test plants. The concentration of the test compound andthe total quantity of solution applied is adjusted to give theapplication concentrations or rates desired. The plants are then allowedto air dry. Mites and aphids are exposed to treated leaves which havebeen left on the plant. Other insect species are exposed to treatedleaves which have been removed from the plant and placed in petri dishescontaining a piece of moist filter paper.

For soil drench applications, the test compound is first dissolved ordispersed in water/acetone as described above, then the amount ofsolution required to give a desired application rate is applied, using apipette, evenly over the top of the soil in the pot. Twenty four hoursafter the treatment, mites and aphids are exposed to leaves which havebeen left on the treated plants. Other insect species are exposed toleaves which have been removed from the plants 24 hours after treatmentand placed in petri dishes containing a piece of moist filter paper.

In direct contact applications, the test compound is, again, firstformulated into a water/acetone solution, as described above, in theconcentrations to be tested. Then the insect to be tested is dippedinto, sprayed with or immersed in the liquid, dried, and observed foreffect.

In the tables below setting forth the experimental data whereapplication rates are given in PPM(parts-per-million), the testformulations are applied either directly to insects or as foliar spraysto plants. Where application rates are given in #/A (pounds per acre)the test formulations are applied as soil drenches. Percent control isthe percent mortality of the insects tested.

CABBAGE LOOPER

Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed,at various application rates, to the test compound applied both by thefoliar spray and soil drench techniques. Leaves are removed from theplants--after approximately 30 minutes of air-drying for the foliarspray application, after 24 hours for the soil drench application--andplaced in petri dishes containing a piece of moist filter paper. Tencabbage loopers, second instar larval stage, are placed in each petridish and the dish covered. Observations of insect mortality are madeafter 48 hours of exposure. Results of these tests are detailed in Table1 below.

                                      TABLE 1                                     __________________________________________________________________________                             Percent Control                                            Application                                                             Test  Rate: PPM                                                                           256                                                                              128                                                                              64                                                                              32 16                                                     Compound                                                                            #/A                32 16 8  4  2                                        __________________________________________________________________________    Product of Example 1                                                                       0 -- --                                                                              -- --                                                                              10 -- -- -- --                                       Product of Example 2.sup.(1)                                                               90                                                                               40.sup.(2)                                                                      5  0  0                                                                               0 0  10 5  5                                        Product of Example 18                                                                     100                                                                              100                                                                              90                                                                              100                                                                              70                                                                              -- -- -- -- --                                       __________________________________________________________________________     Note:                                                                         .sup.(1) average of 2 tests                                                   .sup.(2) Living insects stunted                                          

SOUTHERN ARMYWORM

Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed,at various application rates, to the test compound applied both by thefoliar spray and soil drench techniques. Leaves are removed from theplants--after approximately 30 minutes of air-drying for the foliarspray application, after 24 hours for the soil drench application--andplaced in petri dishes containing a piece of moist filter paper. Tensouthern armyworms, second instar larval stage, are placed in each petridish and the dish covered. Observations of insect mortality are madeafter 48 hours of exposure. Results of these test are detailed in Table2 below.

                                      TABLE 2                                     __________________________________________________________________________                               Percent Control                                          Application                                                             Test  Rate: PPM                                                                           256                                                                              128                                                                              64 32  16                                                   Compound                                                                            #/A                  32                                                                              16                                                                              8 4 2                                          __________________________________________________________________________    Product of Example 1                                                                      0  -- -- --  --                                                                              20                                                                              --                                                                              --                                                                              --                                                                              --                                         Product of Example 2.sup.(1)                                                              100                                                                              95  65.sup.(2)                                                                        15.sup.(2)                                                                      10                                                                               5                                                                              10                                                                              0 15                                                                              0                                          Product of Example 18                                                                     100                                                                              100                                                                              100                                                                              90  70                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                         __________________________________________________________________________     .sup.(1) average of 2 tests                                                   .sup.(2) Living insects stunted                                          

SOYBEAN LOOPER

Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed,at various application rates, to the test compound applied both by thefoliar spray and soil drench techniques. Leaves are removed from theplants--after approximately 30 minutes of air-drying for the foliarspray application, after 24 hours for the soil drench application--andplaced in petri dish containing a piece of moist filter paper. Tensecond instar larval soybean loopers are placed in each petri dish andthe dish covered. Observations of insect mortality are made after 48hours of exposure. Results of these test are detailed in Table 3 below.

                                      TABLE 3                                     __________________________________________________________________________                              Percent Control                                           Application                                                             Test  Rate: PPM                                                                           256                                                                              128                                                                              64 32 16                                                    Compound                                                                            #/A                 32                                                                              16 8 4 2                                          __________________________________________________________________________    Product of Example 1                                                                       0 -- -- -- --                                                                              0 -- --                                                                              --                                                                              --                                         Product of Example 2.sup.(1)                                                               80.sup.(2)                                                                       50.sup.(2)                                                                       25.sup.(2)                                                                      0  0 0 5  0 0 5                                          Product of Example 18                                                                     100                                                                              100                                                                              100                                                                              50 0 --                                                                              -- --                                                                              --                                                                              --                                         __________________________________________________________________________     .sup.(1) average of 2 tests                                                   .sup.(2) Living insects stunted                                          

TOBACCO BUDWORM

Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed,at various application rates, to the test compound applied both by thefoliar spray and soil drench techniques. Leaves are removed from theplants--after approximately 30 minutes of air-drying for the foliarspray application, after 24 hours for the soil drench application--andplaced in petri dishes containing a piece of moist filter paper. Tentobacco budworms, second instar larval stage, are placed in each petridish and the dish covered. Observations of insect mortality are madeafter 48 hours of exposure. Results of these tests are detailed in Table4 below.

                                      TABLE 4                                     __________________________________________________________________________          Application                                                             Test  Rate: PPM                                                                           256 128 64  32  16                                                Compound                                                                            #/A                     32                                                                              16                                                                              8 4 2                                       __________________________________________________________________________    Product of Example 4                                                                      0   --  --  --  --                                                                              0 --                                                                              --                                                                              --                                                                              --                                      Product of Example 5.sup.(1)                                                                95.sup.(2)                                                                        65.sup.(2)                                                                        25.sup.(2)                                                                        20.sup.(2)                                                                      0 5 0 10                                                                              5 15                                      Product of Example 18                                                                     90  70  50  10  10                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                      __________________________________________________________________________     Note:                                                                         .sup.(1) average of 2 tests                                                   .sup.(2) Living insects stunted                                          

MEXICAN BEAN BEETLE

Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed,at various application rates, to the test compound applied both by thefoliar spray and soil drench techniques. Leaves are removed from theplants--after approximately 30 minutes of airdrying for the foliar sprayapplication, after 24 hours for the soil drench application--and placedin petri dishes containing a piece of moist filter paper. Ten mexicanbean beetles second instar larval stage, are placed in each petri dishand the dish covered. Observations of insect mortality are made after 48hours of exposure. Results of these tests are detailed in Table 5 below.

                  TABLE 5                                                         ______________________________________                                                                      Percent Control                                          Application                                                          Test     Rate: PPM  256                                                       Compound #/A                  32                                              ______________________________________                                        Product of Example 1                                                                          10        0                                                   ______________________________________                                    

BOLL WEEVIL

Cotton plants (Deltapine 16), two leaf stage, are exposed, at variousapplication rates, to the test compound applied both by the foliar sprayand soil drench techniques. Leaves are removed from the plants--afterapproximately 30 minutes of air-drying for the foliar spray application,after 24 hours for the soil drench application--and placed in petridishes containing a piece of moist filter paper. Ten adult boll weevilsare placed in each petri dish and the dish is then covered. Observationsof insect mortality are made after 48 hours of exposure. Results ofthese tests are detailed in Table 6 below.

                  TABLE 6                                                         ______________________________________                                                                      Percent Control                                          Application                                                          Test     Rate: PPM  256                                                       Compound #/A                  32                                              ______________________________________                                        Product of Example 1                                                                          10        10                                                  ______________________________________                                    

PEA APHID

Pea plants (Burpee Wando) in the 10-14 day stage are treated with thetest compound, at various application rates, both by foliar spray andsoil drench methods. The plants are air dried for about 30 minutes afterthe foliar spray is applied, then 25-50 pea aphids, adults and nymphs,are put on each treated plant and on an untreated control plant with asmall paint brush. Twenty four hours after a plant has been treated bythe soil drench method, it is infested by 25-50 aphids using thetechnique described above. An untreated control plant is similarlyinfested. After 48 hours of exposure of the insects to the treatedplants, insect mortality is determined by comparison of the number ofinsects on the treated plants to the number on the untreated controlplant. Results of this testing are set forth in Table 7 below.

                  TABLE 7                                                         ______________________________________                                                                      Percent Control                                          Application                                                          Test     Rate: PPM  256                                                       Compound #/A                  32                                              ______________________________________                                        Product of Example 1                                                                            0       0                                                   ______________________________________                                    

TWO SPOTTED MITE

Bush lima bean plants (Burpee Variety 222) in the two-leaf stage aretreated with the test compound, at various application rates, both bythe foliar spray and soil drench methods. The plants are air dried forabout 30 minutes after the foliar spray is applied, then 50-100 twospotted mites, adults and nymphs, are put on each treated plant and onan untreated control plant by placing an untreated infested bean leafcontaining 50-100 mites on the plants. Twentyfour hours after a planthas been treated by the soil drench method, it is infested by 50-100mites using the technique described above. An untreated control plant issimilarly infested. After 48 hours of exposure of the insects to thetreated plants, insect mortality is determined by comparison of thenumber of insects on the treated plants to the number on the untreatedcontrol plant. Results of this testing are set forth in Table 8 below.

                  TABLE 8                                                         ______________________________________                                                                      Percent Control                                          Application                                                          Test     Rate: PPM  256                                                       Compound #/A                  32                                              ______________________________________                                        Product of Example 1                                                                          0         0                                                   ______________________________________                                    

HOUSEFLY

Ten adult Houseflies are placed in a small (2"-3") wire screen cagefitted with a plastic cap. The cage is sprayed with the test compound atthe desired concentration in the form of a solution prepared asdescribed hereinabove. After spraying, the treated cages are storeduntil dry. Sixty minutes after spraying, readings are made of knockdown. The cages are then placed on paper toweling moistened with 5-10%sucrose solution and stored on this toweling for 23 hours at which timethe 24 hours-after-treatment mortality reading is taken. The results ofthis test are given in Table 9 below.

                  TABLE 9                                                         ______________________________________                                                                        Percent Control                               Test     Application                                                          Compound Rate: PPM     256                                                    ______________________________________                                        Product of Example 1                                                                         k        40                                                                   m       100                                                    ______________________________________                                         Note:                                                                         k = 60 minute knockdown                                                       m = 24 hour mortality                                                    

GERMAN COCKROACH

Solutions of test compounds are formulated as described hereinbefore andthe solution which gives a desired application concentration is placedin a flask. Ten german cockroach adults are placed in a teaspoon teastrainer and are dipped into the test solution. The excess solution isshaken off, the tea strainer opened and the insects placed in a clearplastic container containing a small moist piece of dental wick. Thecontainer then is capped with a cover pierced with air holes. Insectmortality is observed 48 hours after the exposure. Results of thistesting are indicated in Table 10 below.

                  TABLE 10                                                        ______________________________________                                                                      Percent Control                                 Test     Application                                                          Compound Rate: PPM  256                                                       ______________________________________                                        Product of Example 1                                                                          0                                                             ______________________________________                                    

SOUTHERN CORN ROOTWORM

A newly germinated corn seed is placed in a one ounce plastic cup fittedwith a snap-on plastic lid and covered with approximately 5 grams ofsterilized soil. The test compound is formulated into solutions asdescribed hereinbefore and applied to the soil as a soil drench at thedesired application rates. After application, the lids are snapped onthe cups and the cups are allowed to stand for about 15 minutes topermit the solution to spread evently through the soil. The lids arethen removed, five second instar rootworm larvae are placed on thetreated soil and the cups recapped. The cup is examined for insectsmortality after 72 hours of exposure. Larvae which cannot crawl or rightthemselves are considered dead. Results of this testing are given inTable 11 below.

                  TABLE 11                                                        ______________________________________                                                               Percent Control                                        Test    Application                                                           Compound                                                                              Rate: #/A  16      1    0.5  0.25  0.125                              ______________________________________                                        Product of Example 1                                                                         100     20      0    0    --                                   Product of Example 2                                                                          90     70     20   30    30                                   ______________________________________                                    

YELLOW FEVER MOSQUITO

Solutions containing the test compound in the desired concentrations areformulated as described hereinabove. Each test solution is placed in a10 ounce foamed polystyrene cup. Approximately ten 3-4 days old yellowfever mosquito larvae are placed in each test solution with aneyedropper. To each solution is then added a very small pinch ofbrewer's yeast and a very small piece of dry food (pulverized solid dogchow). Mortality data are taken after 48 hours of exposure. These dataare shown in Table 12 below.

                  TABLE 12                                                        ______________________________________                                                             Percent Control                                          Test    Application                                                           Compound                                                                              Rate: PPM  10      1.0   0.1    0.01                                  ______________________________________                                        Product of Example 1                                                                         100     100     50     40                                      ______________________________________                                    

I claim:
 1. A compound of the formula ##STR13## wherein R¹ and R² areeach independently selected from the group consisting of halogen, alkyl,haloalkyl, nitro, alkylsulfinyl, alkylsulfonyl and cyano; k and m areintegers from 0 to 3; Q is oxygen; Y is selected from the groupconsisting of oxygen and sulfur; R³ is selected from the groupconsisting of alkyl and ##STR14## wherein R⁵ is selected from the groupconsisting of halogen, alkyl, haloalkyl, nitro and cyano; n is aninteger from 0 to 3; R⁴ is selected from the group consisting of alkyl,alkoxy, alkylthio, amino, alkylamino, dialkylamino and ##STR15## whereinR⁶ is selected from the group consisting of halogen, alkyl, haloalkyl,nitro, and cyano; p is an integer from 0 to 3; and A and B are eachindependently selected from the group consisting of oxygen and sulfur,with the proviso that, if R⁴ is alkoxy, then one of A and B must besulfur.
 2. The compound of claim 1 which is, O,O-diethylO-(xanthen-9-one-2-yl) phosphorothionate.
 3. The compound of claim 1which is, O-ethyl O-(xanthen-9-one-2-yl) S-propyl phosphorothiolate. 4.The compound of claim 1 which is, O-ethyl O-(xanthen-9-thione-2-yl)S-propyl phosphorothiolothionate.
 5. The compound of claim 1 which is,O-ethyl O-(xanthen-9-one-3-yl) S-propyl phosphorothiolothionate.
 6. Thecompound of claim 1 which is, O-ethyl O-(7-nitroxanthen-9-one-2-yl)S-propyl phosphorothiolothionate.
 7. The compound of claim 1 which is,O-ethyl O-(3-chloroxanthen-9-one-2-yl) S-propyl phosphorothiolothionate.8. The compound of claim 1 which is, O-ethylO-(7-cyanoxanthen-9-one-2-yl) S-propyl phosphorothiolothionate.
 9. Thecompound of claim 1 which is O-ethyl O-(3-chloroxanthen-9-one-2-yl)S-propyl phosphorothiolate.
 10. The compound of claim 1 which is O-ethylO-(xanthen-9-thione-2-yl) S-propyl phosphorothiolothionate.
 11. Thecompound of claim 1 which is O-ethyl O-(3-chloroxanthen-9-thione-2-ylS-propyl phosphorothiolate.